Bis-hydantoin dialcohols

ABSTRACT

Dialcohols of dinuclear, five-membered or six membered, unsubstituted or substituted N-heterocyclic compounds which contains two NH-groups in the molecule are prepared by reacting dinuclear, five-membered or six-membered, unsubstituted or substituted N-heterocyclic compounds, for example bis(hydantoin)- or bis-(dihydrouracil) compounds, with styrene oxide to give dialcohols. A preferable class of hydantoin alcohols are those having the formula:   WHEREIN R1 and R2 is hydrogen, alkyl of 1 to 5 carbon atoms, or wherein R1 and R2 is tetramethylene or pentamethylene, and A is an alkylene of 1 to 12 carbon atoms or lower alkylene interrupted by one oxygen atom; and m and n each represents an integer having a value of 1 to 30. These compounds are useful as intermediates for the preparation of diglycidyl compounds. The preparation and use of the diglycidyl compounds is described in Offenlegungsschrift 2,056,789 which issued May 27, 1971.

United States Patent 191 Habermeier et al.

[ May 6, 1975 BlS-HYDANTOIN DIALCOHOLS [75] Inventors: Juergen l-labermeier, Allschwil; Hans Batzer, Arlesheim; Daniel Porret, Binningen, all of Switzerland Ciba-Geigy Corporation, Ardsley, NY.

[22] Filed: June 13, 1972 [2]] Appl. No.: 262,423

Related 05. Application Data [63] Continuation-in-part of Ser. No. 80,493, Oct. I3,

1970, Pat. No. 3,726,895.

[73] Assignee:

Primary Examiner-Natalie Trousof Attorney. Agent. or Firm Vincent J. Cavalren [57] ABSTRACT II II H (0-fH-CH m [30] Foreign Application Priority Data Nov. 18, i969 Switzerland l7l05/69 [52] US. Cl. 260/3095 [51] Int. Cl C07d 49/32 [58] Field of Search 260/3095 [56] References Cited UNITED STATES PATENTS 3,391,097 7/1968 Williamson 260/3095 zen 309.5

3,449,353 6/1969 Porret et al...

3,542,803 11/1970 Porret 260/3095 3,592,823 7/1971 Porret 260/3095 3,629,263 l2/l97l Batzer et al 260/3095 wherein R, and R is hydrogen, alkyl of 1 to 5 carbon atoms, or wherein R, and R is tetramethylene or pentamethylene, and A is an alkylene of 1 to 12 carbon atoms or lower alkylene interrupted by one oxygen atom; and m and n each represents an integer having a value of l to 30. These compounds are useful as intermediates for the preparation of diglycidyl compounds. The preparation and use of the diglycidyl compounds is described in Offenlegungsschrift 2,056,789 which issued May 27, 1971.

6 Claims, No Drawings 1 2 BlS-HYDANTOIN DIALCOHOLS wherein 2.. Z, and Ahave the same meaning as in For mula (I), with styrene oxide in the presence of a suit This application is a continuation in part application able catalyst. of Copending application 80,493, filed The addition of styrene oxide to both NH groups of Oct. l3. l 70. no US fl 5 the binuclear N-heterocyclic compounds of formula Subject of P invention are new dilll- (ll)lcan be carried out both in the presence of acid cat- C l 0f th g n al fOrmuli! alysts and of alkali catalysts, with a slight excess over O 1 0 ll 1 lll-l(O-CH-CH /CN A N c\ (CH cu o u c=0 0=c l 2 2 (5 kn: NJ

wherein Z and Z independently of one another each the equivalent amount of the styrene oxide being emdenotes a nitrogen-free divalent radical which is necesployed per equivalent of NH group of the binuclear N- sary to complete a five-membered or six-membered, heterocyclic compound of formula (II). unsubstituted or substituted heterocyclic ring, A repre- Preferablw however alkaline Catalysts such as leml" sents a divalent aliphatic, cycloaliphatic or araliphatic t yl mm nium chlo e or tertiary amines are used radical. and in particular preferably represents an alin the manufacture of (alcohols of formula U) n kylene radical or an alkylene radical which is intern which the sum of m and n is 2. HOWCVfil, alkali halides, rupted by oxygen atoms and m and 11 each represent an Such as lithium chloride or sodium chloride, can also be integer having a value of 1 to 30, preferably of l to 4. Successfully used for this addition reaction; it also takes The radical Z in the formula (1) preferably only conplace without catalysts. sists of carbon and hydrogen or of carbon, hydrogen when manufacturing diaICOhOIS of formula in and oxygen It can for example be a radical of formulae which th um f m n n i greater h n i i pr f rable to startfrom the simple dialcohols of formula (I) in which m and n are each I, with further styrene oxide being added to both OH groups of this compound in the (3:0 C C=O 3s presence of acid catalysts.

/ The binuclear N-heterocyclic compounds of formula R' (ll) used for the manufacture of the new styrene oxide C addition products of formula (I) are above all bisn (hydantoin) compounds or bis-(dihydrouracil) com- 40 pounds in which the two N heterocyclic rings are R linked to another via an alkylene bridge, for example a methylene group which is bonded to one endocyclic C-R' or C nitrogen atom of each of the heterocyclic rings in quesl tion R A first class of such bis-(hydantoin) compounds cor m responds to the general formula C Q 0 \RIIH E:

H N CH 1 \ll-l h l 1 wherein R, R", R' and R"" independently ofone an- 2 (I; other each can denote a hydrogen atom or, for exam- C l C C-O ple, an alkyl radical. an alkenyl radical, a cycloalkyl R R radical or an optionally substituted phenyl radical. 1 2 R R The new dialcohols of formula (I) can be manufac- 3 tured by reacting binuclear N-heterocyclic compounds wherein R,, R R and R each denote a hydrogen atom of general formula or a lower alkyl radical with l to 4 carbon atoms, or

wherein R, and R or R and R together form a tctramethylene or pentamethylene radical.

l.l '-methylene-bis-( 5,5-dimethyl-hydantoin l.l methylene-bis-( 5-methyI-S-ethyI-hydantoin l l methylene-bis-(5-propyl-hydantoin). l,l'-methylenebis-(S-isopropylhydantoin) may for example be mentioned.

another each denote a hydrogen atom or a lower alkyl radical with l to 4 carbon atoms.

1,l '-Methylene-bis-(5,6-dihydrouracil), l,l methylene-bis-(6-methyl-5,-dihydrouracil) and l,1'- methylene-bis-(S,5-dimethyl5,o-dihydrouracil) may be mentioned.

As aspect of this invention is as follows:

a to-cfa-ca -1 -ca l1 ir- (CH2TH0) H c=o 61 1 Z\ G? 1 2 (b) c c a tofu-cs A- (ca -ia-o a A further class of such bis-(hydantoin) compounds corresponds to the general formula wherein R is an aliphatic. cycloaliphatic or araliphatic radical. especially an alkyl radical, or an alkylene radical which is interrupted by oxygen atoms. and R, R R and R each denote a hydrogen atom or a lower alkyl radical with l to 4 carbon atoms, or wherein R. and R or R and R together form a tetramethylene or pentamethylene radical. Bis-(5,5-dimethyl-l1ydantoinyl-3)- methane, l ,2-bis( 5', 5'-dimethyl-hydantoinyl-3 ethane, 1,4-bis-(5', 5 '-dimethyl-hydantoinyl3 butane, l,6-bis-( 5 5'-dimethyl-hydantoinyl-3 hexane, l.l 2-bis-( 5 5 '-dimethyl-hydantoinyl3 dodecane and B,B'-bis-(5', 5'-dimethyl-hydantoinyl- 3')-diethyl-ether may be mentioned.

A preferentially employed class of bis- (dihydrouracil) compounds corresponds to the general formula wherein R and R is hydrogen, alkyl of l to 5 carbon atoms, or wherein R, and R tetramethylene or pentamethylene; and A is an alkylene of l to 12 carbon atoms or lower alkylene interrupted by one oxygen atom; and m and 11 each represents an integer having a value of l to 30. The dialcohols are useful as intermediates for the preparation of diglycidyl compounds, The preparation and use of the diglycidyl compounds are described in Offenlegungsschrift 2,056,789 which issued on May 27, 1971. The diglycidyl ethers can be manufactured by reacting the dialcohols in one stage or several stages, in a manner which is in itself known, with an epihalogenohydrin or B-methylepihalogenohydrin, such as, for example, epichlorohydrin, B-methylepichlorohydrin or epibromhydrin.

In the single stage process, the reaction of epihalogenohydrin with the dialcohols takes place in the presence of of alkali, with sodium hydroxide or potassium hydroxide being preferably used. In this single-stage process, the epichlorohydrin which is reacted according to the process can be wholly or partially replaced by dichlorohydrin. which under the process conditions and on appropriate addition of alkali is transiently converted to epichlorohydrin and then reacted as such with the dialcohol. ln the 2-stage process which is preferably used, the dialcohols undergo an addition reaction with an epihalogenohydrin in the presence of acid or basic catalysts to give the halogenohydrin ether and thereafter the latter is dehydrohalogenated in a second stage by means of alkali, such as, potassium hydroxide or sodium hydroxide, to give the glycidyl ether Suitable acid catalysts for the Z-stage processes are especially loose acids, such as, for example, AlCl SfCl SnCl FeCl BF ZnCland their complexes with organic compounds.

The reaction can also be accelerated by the addition of other suitable catalysts, for example, alkali hydroxides, such as, sodium hydroxide, alkali halides, such as, lithium chloride, sodium chloride, bromide and fluoride. The diglycidyl ethers react with the customary curing agents for polyepoxide compounds and can therefore be crosslinked or cured by addition of such dipping resins. casting resins. injection molding formul lations, impregnating resins and binders, adhesives. as tooling resins, laminating resins. ceiling and filling compositions, floor covering compositions and binders for mineral aggregates.

EXAMPLE l l,] '-Methylene-bis-[ 3-(B-hydroxy-B-phenylethyl )-5,5- dimethylhydantoin] L2 Protons at 2 Protons at 5 4 Protons at 5 2 Protons at 6' 2 Protons l0 Protons at 6 ll-O-CIl-Cli N 267.5 g of styrene oxide are added dropwise at 120C over the course of l k hours, with good stirring, to a solution of 268.25 g of L1 '-methylene-bis-(5,5- dimethylhydantoin) [1 mol and 1.3 g oflithium chloride in 1.5 litres of dimethylformamide. Thereafter the mixture was stirred for a further 2 hours at l C. The

phenylethyl)-5,5-dimethylhydantoin] purified in this way melts at I40 142C.

foun l 1.06 6.39

Elementury analysis shows: calculate ll.02 it 6.34 1

The infrared spectrum shows, through the absence of absorptions of the NH grouping and through the presence of the following bands, that the desired substance has been produced:

3450 cm (OH); 1769 cm and 1708 cm (C=O) and 702 cm (aromatic).

Furthermore, the proton-magnetic resonance spectrum Mc HNMR, recorded in CDCL', at 35C, with tetramethylsilane (TMS) as the standard) shows that the new compound has the structure given below. Integration shows 32 protons (theory: 32).

1.28 (singlet) 2 x 3.52-3.70 (multiplet): 2 x C OH 3.75-3.90 (quartet): 2 x/N-C l I C 4.92-5.05 (multiplet) 2 x H H 7.27 (singlet) 2 x H CH) H30 h u on -N/ N cs on EXAMPLE 2 l,l '-Methylene-bis-[3-(B-hydroxy-B-phenylethyl)-5- isopropylhydantoin] 79.5 g of styrene oxide (0.66 mol) are added dropwise over the course of 2 hours at l27-l3]C, with vigorous stirring, to a mixture of 89 g of LI methylene-bis-(S-isopropylhydantoin) (0.3 mol), 500 ml of dimethylformamide and 0.37 g of lithium chloride. Thereafter the mixture is stirred for a further 3 hours at l30C The pale yellow solution is filtered hot and is subsequently concentrated at C on a rotary evaporator, under 20 mm Hg. The residue is now dried to constant weight at 90C/0.l mm Hg. l60.4 g ofa viscous, yellow, clear substance are obtained. This corresponds to 99.3 of theory.

EXAMPLE 3 Addition of styrene oxide to 1.1'-methylene-bis-[3-(B-hydroxy-B-phenylethyl)-5,5- dimethylhydantoin] H- (OCii-Cli -N N 45.6 g of the product manufactured according to Example 1 (0.897 mol) are dissolved in 500 ml of anhydrous dioxane. 3.5 ml of a 47 7( strength boron fluoride-diethyl etherate solution in diethyl ether are then added and the mixture is warmed to 80C whilst stirring. 192 g of styrene oxide (1.6 mols) are now added dropwise over the course of 40 minutes. The reaction becomes exothermic; the temperature of the reaction mixture rises to 84C after the heating bath has been removed. Thereafter the reaction mixture is stirred for a further 2 hours at 90C. adjusted to a pH of 7.0 (initial value: pH 3) with the aid of strength aqueous sodium hydroxide solution. brought to room temperature and filtered. The filtrate is concentrated on a rotary evaporator at 70C under a water pump vacuum and dried to constant weight at 85C/0.l mm Hg. 198 g of a light yellow, viscous substance are obtained. From this yield, the amount of styrene oxide added can be defined as 152.4 g, corresponding to 1.266 mols. Thus approx. 14 molecules of styrene oxide are added per starting molecule.

This is in agreement with combustion analysis. Herein a nitrogen content of 2.4 70 is found, the theoretically calculated value being 2.5 N. The protonmagnetic resonance spectrum (60 Mc H-NMR, re-

corded in CDCl at C with tetramethylsilane (TMS) as the standard) also confirms these relationships. Ifthe proton number of the signal of the CH. j

groups (6 1.27) is compared with the proton number of the signal for the aromatic protons, it is found that 16 styrene oxide molecules are present per 1.1-

methylene-bis-(S,S-dimethylhydantoin) molecule. Thus 14 mols of styrene oxide are added per starting molecule. Accordingly the adduct has the following structure.

-.l* CH l il H C l i CH -N N-(Cil -CHO) -H m 2 Y 2 n EXAMPLE4 2.2'-Bis-| l-(B-hydroxy-B-phenylethyl1-5.5- dimethylhydantoinyl-3 l-diethyl ether A solution of 130.8 g of 2.2'-bis-(5,5-

dimethylhydantoinyl-3)-diethyl ether (0.4 mol) in 800 ml of dimethylformamide is treated with 0.5 g of lithium chloride and warmed to 140C whilst stirring. 106.0 g of styrene oxide (0.66 mol) are added dropwise at this temperature over the course of 3 hours. Thereafter the mixture is stirred for a further 10 hours at 150C. cooled to 60C. filtered and concentrated on a rotary evaporator at 60C/waterpump vacuum; thereafter the material is dried to constant weight at C/0.2

mm Hg.

225.8 g of a light brown. glassy brittle mass are obtained. corresponding to 99.5 7r of theory. Combustion analysis shows a nitrogen content of 10.00 71 (theory 10.00 72 N). The proton-magnetic resonance spectrum (60 Mc H-NMR. recorded in CDCl at 35C. internal standard: TMS) is also in agreement with the structure given below, and above all the ratio of the protons at 5 1.3 to those of 6 7.3 is 12:10. which also indicates that the reaction takes place quantitatively:

N-Cil "CH -O-Cii -CIi N N-CH -ClI-Oli EXAMPLE 5 1,12-Bis-l l '-(B-hydroxy-fi-phenylethyl)-5', 5 '-dimethylhydantoinyl-3 l-dodecane 50.6 g of 1.12-bis-(5', 5'-dimethylhydantoinyl-3)- dodecane (0.12 mol) together with 500 ml of dimethylformamide and 0.2 g of lithium chloride are stirred at C. 31.8 g of styrene oxide (0.265 mol) are added dropwise over the course of 2 hours. Thereafter the mixture is stirred for a further 12 hours at l48-153C. Working up is carried out in accordance with Example 4. 79.4 g of a light brown, glassy mass are obtained. corresponding to 99.9% of theory.

3,882,137 9 10 We claim: methylene-bis-l3-(B-hydroxy-B-phenylethyl)-5.5 l. A dialcohol of the formula dimethylhydantoin] wherein R and R is hydrogen, alkyl of l to 5 carbon 4. A compound as claimed in claim 1 which is l.] atoms, or where R and R is tetramenthylene or pentamethylene-bis-l 3-(B-hydroxy-B-phenylethyl )-5- methylene; and A is an alkylene of I to l2 carbon isopropylhydantoin].

atoms or lower alkylene interrupted by one oxygen 5. A compound as claimed in claim 1 which is 2.2- atom; and m and n each represents an integer having bis-[ l-(B-hydroxyfl-phenylethyl)-5,5- a value of l to 30. dimethylhydantoinyl-3]-diethyl ether.

2. A compound as claimed "'1 claim 1 wherein m and p as C alme C w m n each represents an integer having a value of l to 4. bis'l l fi 'fi dimethylhydantoinyl-3 ]dodecane.

3. A compound as claimed in claim 1 which is 1,] 

1. A DIALCOHOL OF THE FORMULA H-(O-CH(-C6H5)-CH2)M-(2,5-DI(O=),4-R1,4-R2-IMIDAZOLIDIN1,3-YLENE)-CH2-(2,5 -DI(O=),4-R1,4-R2-IMIDAZOLIDIN-3,1YLENE)-(CH2-CH(-C6H5)-O)N-H WHEREIN R1 AND R2 IS HYDROGEN, ALKYL OF 1 TO 5 CARBON ATOMS, OR WHERE R1 AND R2 IS TETRAMENTHLENE OR PENTAMETHYLENE; AND A IS AN ALYLENE OF TO 12 CARBON ATOMS OR LOWER ALKYLENE INTERRUPTED BY ONE OXYGEN ATOM; AND M AND N EACH REPRESENTS AN INTEGER HAVING A VALUE OF TO
 30. 2. A compound as claimed in claim 1 wherein m and n each represents an integer having a value of 1 to
 4. 3. A compound as claimed in claim 1 which is 1,1''-methylene-bis-(3-( Beta -hydroxy- Beta -phenylethyl)-5,5-dimethylhydantoin).
 4. A compound as claimed in claim 1 which is 1,1''-methylene-bis-(3-( Beta -hydroxy- Beta -phenylethyl)-5-isopropylhydantoin).
 5. A compound as claimed in claim 1 which is 2,2''-bis-(1-( Beta -hydroxy- Beta -phenylethyl)-5,5-dimethylhydantoinyl-3)-diethyl ether.
 6. A compound as claimed in claim 1 which is 1,12-bis-(1''-( Beta -hydroxy- Beta -phenylethyl)-5,5-dimethylhydantoinyl-3'')-dodecane. 